共价有机框架材料的离子化改性及其催化合成环碳酸酯的性能研究

引用本文: 张衍, 胡慧, 居佳, 闫欠欠, Vasanthakumar Arumugam, 景学超, 蔡华强, 高艳安. 共价有机框架材料的离子化改性及其催化合成环碳酸酯的性能研究[J]. 催化学报, 2020, 41(3): 485-493. doi: S1872-2067(19)63487-X shu

Citation: Yan Zhang, Hui Hu, Jia Ju, Qianqian Yan, Vasanthakumar Arumugam, Xuechao Jing, Huaqiang Cai, Yanan Gao. Ionization of a covalent organic framework for catalyzing the cycloaddition reaction between epoxides and carbon dioxide[J]. Chinese Journal of Catalysis, 2020, 41(3): 485-493. doi: S1872-2067(19)63487-X shu

共价有机框架材料的离子化改性及其催化合成环碳酸酯的性能研究

a 中国工程物理研究院化工材料研究所, 四川绵阳 621900;
b 海南大学热带岛屿资源先进材料教育部重点实验室, 海南海口 570228;
c 聊城鲁西聚碳酸酯有限公司, 山东聊城 252000
基金项目:
国家自然科学基金（21473196，21702194）；海南大学科研启动基金（KYQD（ZR）1856）.

摘要: 共价有机框架（COFs）材料是继金属-有机框架材料之后，在拓扑学基础上发展起来的又一类多孔材料.这类材料是由轻质元素（C，H，O，N，B，Si等）通过可逆共价键连接而成的结晶性有机多孔聚合物，具有比表面积大、骨架密度低、孔道结构规整、可人为设计以及表面易修饰改性等特点，自2005年首次报道以来就引起了人们的广泛关注.经过十多年的发展，COFs材料已经被广泛用于气体吸附/分离、光电、能量存储、非均相催化等研究领域.由于材料的多孔性以及相对稳定的特点，近年来COFs材料作为催化剂或催化剂载体用于多相催化反应已经成为该领域的一个研究热点.但是到目前为止，COFs材料的离子化改性用于异相催化相关研究还相对较少.本文选择二维骨架中含有羟基基团的H₂P-DHPh COF作为载体，通过两步接枝反应成功地将咪唑型离子液体引入到COF材料的孔道中采用红外光谱、核磁共振、粉末X射线衍射、热失重分析等方法详细地表征了COF材料在后修饰过程中的变化.研究发现，1，4-二溴丁烷与N-甲基咪唑基团的引入占据了部分孔道，导致框架材料的孔径和孔容减小.同时，我们还将该改性后的离子型COF材料在DMSO/盐酸溶液中消解，利用核磁共振波谱计算了离子化程度.实验结果表明，N-甲基咪唑的接枝率约为4.9 wt%.在既定的反应条件下，将该离子化的COF材料作为多相催化剂用于CO₂和环氧化合物之间的环加成反应.以环氧氯丙烷作为测试底物，发现该离子型催化剂的催化性能与H₂P-DHPh COF相比有大副度提高，转化率达到了91%（120℃，24h，CO₂压力位1.0MPa）.在相同的条件下，该催化剂还对其他的环氧化合物具有一定的催化效果，其中环氧丙烷的转化率高达95%，且目标产物碳酸丙烯酯的选择性为100%.然而，对于大分子的环氧化合物，转化率和产率均较低，表明催化剂具有明显的尺寸选择性.此外，我们还以环氧氯丙烷的环加成反应为例考察了催化剂的循环稳定性，经过连续的5次循环，催化剂的催化活性得到了有效保持.我们的研究表明COF材料作为异相催化剂用于多相催化具有潜在的应用前景.而且，由于离子型多孔材料具有可交换的性质，我们可以通过将不同功能的反离子交换到孔道中，从而得到具有不同功能特性的多孔材料.因此，离子化共价有机框架材料是一类集多孔、高比表面积、可人为设计等性质于一体的新型多孔材料，有望应用于更加广泛的研究领域.

关键词:

English

Ionization of a covalent organic framework for catalyzing the cycloaddition reaction between epoxides and carbon dioxide

a Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900, Sichuan, China;
b Key Laboratory of Ministry of Education for Advanced Materials in Tropical Island Resources, Hainan University, Haikou 570228, Hainan, China;
c Liaocheng Luxi Polycarbonate Co. Ltd, Liaocheng 252000, Shandong, China
Received Date: 29 June 2019
Revised Date: 25 July 2019

Abstract: Covalent organic frameworks (COFs), with two dimensional (2D-) or three dimensional (3D-) structures, have accessible open channels or nanopores, with uniform sizes ranging from angstroms to nanometers and have emerged as an excellent and promising platform for designing catalysts or catalyst carriers. Herein, a 2D-COF grafted with a 1-alkyl-3-methylimidazolium-based ionic liquid (AMIMBr@H₂P-DHPh COF) on the channel walls was synthesized and utilized as a highly efficient heterogeneous catalyst for the chemical fixation of CO₂ via a reaction with epoxides under solvent-free and co-catalyst-free conditions. The as-synthesized AMIMBr@H₂P-DHPh COF shows excellent catalytic activity in promoting the cycloaddition reactions between epoxide and CO₂; the excellent catalytic activity was maintained for up to five cycles. Advantages like high porosity, functional versatility, easy modification of COFs, and high catalytic activity of ionic liquids, have been realized in a single material.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

共价有机框架材料的离子化改性及其催化合成环碳酸酯的性能研究

English

Ionization of a covalent organic framework for catalyzing the cycloaddition reaction between epoxides and carbon dioxide

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

共价有机框架材料的离子化改性及其催化合成环碳酸酯的性能研究

English

Ionization of a covalent organic framework for catalyzing the cycloaddition reaction between epoxides and carbon dioxide

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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